Zhaohui Aleck Wang

The biogeochemistry of carbon across a gradient of streams and rivers within the Congo Basin

Dissolved organic carbon (DOC) and inorganic carbon (DIC and pCO2), lignin biomarkers and the optical properties of dissolved organic matter (DOM) were measured in a gradient of streams and rivers within the Congo Basin (Republic of Congo), with the aim of examining how vegetation cover and hydrology influences the composition and concentration of exported fluvial carbon (C). Three sampling campaigns (February 2010, November 2010 and August 2011) spanning 56 sites are compared by sub-basin watershed land cover type (savannah, tropical forest, and swamp) and hydrologic regime (high, intermediate, and low). Land cover properties predominately controlled the amount and quality of DOC, chromophoric DOM (CDOM) and lignin phenol concentrations (∑8) exported in streams and rivers throughout the Congo Basin. Higher DIC concentrations and changing DOM composition (lower molecular weight, less aromatic C) during periods of low hydrologic flow indicated a shift from rapid overland supply pathways in wet conditions to deeper groundwater inputs during drier periods. Lower DOC concentrations in forest and swamp sub-basins were apparent with increasing catchment area, indicating enhanced DOC loss with extended water residence time. Surface water pCO2 in savannah and tropical forest catchments ranged between 2600 and 11922 µatm, and swamp regions contained extremely high pCO2 (10598-15802 µatm), highlighting their potential as significant pathways for water-air efflux. Our data suggest that the quantity and quality of DOM exported to streams and rivers is largely driven by terrestrial ecosystem structure and that anthropogenic land-use or climate change may impact the composition and reactivity of fluvial C, with ramifications for regional C budgets and future climate scenarios.

A long pathlength liquid-core waveguide sensor for real-time pCO2 measurements at sea

An improved spectrophotometric pCO2 sensor based on a long pathlength liquid-core waveguide is described for pCO2 underway measurements. A low refractive index (RI) amorphous fluoropolymer (Teflon AF 2400) tubing, the heart of the sensor, served as both a CO2-permeable membrane equilibrator and a long pathlength liquid-core waveguide spectrophotometric cell. By using absorbance ratios at three wavelengths and carefully preparing and storing indicator solution, good reproducibility and long-term stability were achieved. The sensor behaved closely to theoretical prediction. Two pronounced features of the sensor were fast response (approximately 2 min to reach 99% of full response) due to high permeability of the Teflon AF, and high precision (about ±2–3 μatm in the pCO2 range of 200–500 μatm) due to the long pathlength. The temperature dependence of the sensor is also discussed. The sensors measurements agreed well with the “showerhead equilibrator plus infrared detector” method during an underway survey of sea surface pCO2 along a transect off the Georgia coast in December 2000. Besides underway mapping, the sensor shows broad applicability for measuring pCO2 in different environments.

Automated Spectrophotometric Analyzer for Rapid Single-Point Titration of Seawater Total Alkalinity

An automated analyzer was developed to achieve fast, precise, and accurate measurements of seawater total alkalinity (AT) based on single-point titration and spectrophotometric pH detection. The single-point titration was carried out in a circulating loop, which allowed the titrant (hydrochloric acid and bromocresol green solution) and a seawater sample to mix at a constant volume ratio. The dissolved CO2 in the sample-titrant mixture was efficiently removed by an inline CO2 remover, which consists of a gas-permeable tubing (Teflon AF2400) submerged in a sodium hydroxide (NaOH) solution. The pH of the mixture was then measured with a custom-made spectrophotometric detection system. The analyzer was calibrated against multiple certified reference materials (CRMs) with different AT values. The analyzer features a sample throughput time of 6.5 min with high precision (±0.33-0.36 μmol kg(-1); n = 48) and accuracy (-0.33 ± 0.99 μmol kg(-1); n = 10). Intercomparison to a traditional open-cell AT titrator showed overall good agreement of 0.88 ± 2.03 μmol kg(-1) (n = 22). The analyzer achieved excellent stability without recalibration over 11 days, during which time 320 measurements were made with a total running time of over 40 h. Because of its small size, low power consumption requirements, and its ability to be automated, the new analyzer can be adapted for underway and in situ measurements.

In Situ Sensor Technology for Simultaneous Spectrophotometric Measurements of Seawater Total Dissolved Inorganic Carbon and pH

A new, in situ sensing system, Channelized Optical System (CHANOS), was recently developed to make high-resolution, simultaneous measurements of total dissolved inorganic carbon (DIC) and pH in seawater. Measurements made by this single, compact sensor can fully characterize the marine carbonate system. The system has a modular design to accommodate two independent, but similar measurement channels for DIC and pH. Both are based on spectrophotometric detection of hydrogen ion concentrations. The pH channel uses a flow-through, sample-indicator mixing design to achieve near instantaneous measurements. The DIC channel adapts a recently developed spectrophotometric method to achieve flow-through CO2 equilibration between an acidified sample and an indicator solution with a response time of only ∼ 90 s. During laboratory and in situ testing, CHANOS achieved a precision of ±0.0010 and ± 2.5 μmol kg(-1) for pH and DIC, respectively. In situ comparison tests indicated that the accuracies of the pH and DIC channels over a three-week time-series deployment were ± 0.0024 and ± 4.1 μmol kg(-1), respectively. This study demonstrates that CHANOS can make in situ, climatology-quality measurements by measuring two desirable CO2 parameters, and is capable of resolving the CO2 system in dynamic marine environments.

High-frequency spectrophotometric measurements of total dissolved inorganic carbon in seawater.

A new spectrophotometric method was developed to achieve continuous measurements of total dissolved inorganic carbon (DIC) in seawater. It uses a countercurrent flow design and a highly CO2-permeable membrane (Teflon AF 2400) to achieve flow-through CO2 equilibration between an acidified sample and an indicator solution with a fast response time of ~22 s. This method improves the spatiotemporal resolution by more than 1 order of magnitude compared to the existing spectrophotometric method. The flow-through equilibration allows for continuous (~1 Hz) detection and real-time data smoothing. The method had a short-term precision of ± 2.0 μmol kg(-1) for a given flow-through sample. It achieved a field precision of ± 3.6 μmol kg(-1) and successfully captured high DIC variability down to minute scales. Measurements by the new method over the typical range of oceanic DIC showed good agreement with measurements made by an established method (mean differences -1.6 to 0.3 μmol kg(-1) with 1σ ± 6.0-6.7 μmol kg(-1)). This level of precision and accuracy is comparable to that of the existing spectrophotometric method. The characteristics of the new method make it particularly suitable for high-frequency, submerged measurements required for mobile observing platforms in the ocean. It can also be adapted for high-frequency, spectrophotometric measurements of seawater CO2 fugacity.

Changes in anthropogenic carbon storage in the Northeast Pacific in the last decade

In order to understand the oceans role as a sink for anthropogenic carbon dioxide (CO2), it is important to quantify changes in the amount of anthropogenic CO2 stored in the ocean interior over time. From August to September 2012, an ocean acidification cruise was conducted along a portion of the P17N transect (50°N 150°W to 33.5°N 135°W) in the Northeast Pacific. These measurements are compared with data from the previous occupation of this transect in 2001 to estimate the change in the anthropogenic CO2 inventory in the Northeast Pacific using an extended multiple linear regression (eMLR) approach. Maximum increases in the surface waters were 11 µmol kg−1 over 11 years near 50°N. Here, the penetration depth of anthropogenic CO2 only reached ∼300 m depth, whereas at 33.5°N, penetration depth reached ∼600 m. The average increase of the depth-integrated anthropogenic carbon inventory was 0.41 ± 0.12 mol m−2 yr−1 across the transect. Lower values down to 0.20 mol m−2 yr−1 were observed in the northern part of the transect near 50°N and increased up to 0.55 mol m−2 yr−1 toward 33.5°N. This increase in anthropogenic carbon in the upper ocean resulted in an average pH decrease of 0.002 ± 0.0003 pH units yr−1 and a 1.8 ± 0.4 m yr−1 shoaling rate of the aragonite saturation horizon. An average increase in apparent oxygen utilization of 13.4 ± 15.5 µmol kg−1 centered on isopycnal surface 26.6 kg m−3 from 2001 to 2012 was also observed.

The effect of elevated carbon dioxide on the sinking and swimming of the shelled pteropod Limacina retroversa

The effect of elevated carbon dioxide on the sinking and swimming of the shelled pteropod Limacina retroversa Alexander J. Bergan, Gareth L. Lawson*, Amy E. Maas, and Zhaohui Aleck Wang Biology Department, Woods Hole Oceanographic Institution, Woods Hole, MA, USA Bermuda Institute of Ocean Sciences, St. George’s GE01, Bermuda Marine Chemistry and Geochemistry Department, Woods Hole Oceanographic Institution, Woods Hole, MA, USA *Corresponding author: tel: þ508 289 3713; fax: 508 457 2134; e-mail: glawson@whoi.edu.

Carbon Budget of Tidal Wetlands, Estuaries, and Shelf Waters of Eastern North America

Carbon cycling in the coastal zone affects global carbon budgets and is critical for understanding the urgent issues of hypoxia, acidification, and tidal wetland loss. However, there are no regional carbon budgets spanning the three main ecosystems in coastal waters: tidal wetlands, estuaries, and shelf waters. Here, we construct such a budget for Eastern North America using historical data, empirical models, remote-sensing algorithms, and process-based models. Considering the net fluxes of total carbon at the domain boundaries, 59 ± 12% (± 2 standard errors) of the carbon entering is from rivers and 41 ± 12% is from the atmosphere, while 80 ± 9% of the carbon leaving is exported to the open ocean and 20 ± 9% is buried. Net lateral carbon transfers between the three main ecosystem types are comparable to fluxes at the domain boundaries. Each ecosystem type contributes substantially to exchange with the atmosphere, with CO2 uptake split evenly between tidal wetlands and shelf waters, and estuarine CO2 outgassing offsetting half of the uptake. Similarly, burial is about equal in tidal wetlands and shelf waters, while estuaries play a smaller but still substantial role. The importance of tidal wetlands and estuaries in the overall budget is remarkable given that they respectively make up only 2.4 and 8.9% of the study domain area. This study shows that coastal carbon budgets should explicitly include tidal wetlands, estuaries, shelf waters and the linkages between them; ignoring any of them may produce a biased picture of coastal carbon cycling.

Seasonal controls of aragonite saturation states in the Gulf of Maine

The Gulf of Maine (GoME) is a shelf region especially vulnerable to ocean acidification (OA) due to natural conditions of low pH and aragonite saturation states (Ω-Ar). This study is the first to assess the major oceanic processes controlling seasonal variability of the carbonate system and its linkages with pteropod abundance in Wilkinson Basin in the GoME. Two years of seasonal sampling cruises suggest that water-column carbonate chemistry in the region undergoes a seasonal cycle, wherein the annual cycle of stratification-overturn, primary production, respiration-remineralization and mixing all play important roles, at distinct spatiotemporal scales. Surface production was tightly coupled with remineralization in the benthic nepheloid layer during high production seasons, which results in occasional aragonite undersaturation. From spring to summer, carbonate chemistry in the surface across Wilkinson Basin reflects a transition from a production-respiration balanced system to a net autotropic system. Mean water-column Ω-Ar and abundance of large thecosomatous pteropods show some correlation, although patchiness and discrete cohort reproductive success likely also influence their abundance. Overall, photosynthesis-respiration is the primary driving force controlling Ω-Ar variability during the spring-to-summer transition as well as over the seasonal cycle. However, calcium carbonate (CaCO3) dissolution appears to occur near bottom in fall and winter when bottom water Ω-Ar is generally low but slightly above 1. This is accompanied by a decrease in pteropod abundance that is consistent with previous CaCO3 flux trap measurements. The region might experience persistent subsurface aragonite undersaturation in 30–40 years under continued ocean acidification.